Substantive triazine azo dyes



Patented Jan. 18, 1949 SUBSTANIIVE TRIAZI NE DYES Ernst Keller and Reinhard Zweidler, Basel, Switzerland, assignors to I. It. Geigy Switzerland, a Swiss firm, p

A. G., Basel,

.. t No Drawing. Application August 28, 1944, Serial No. 551,622. In Switzerland September 1, 1943 1 We have found that valuable new "compounds of the stilbene or dibenzyl series respectively are obtained, when condensation products of the general formula wherein are caused to react with aromatic amines with the condition that at least one halogen atom is replaced by the radical of an aminoazo compound or of an amine cap-able of forming azo dyestuffs and that the other halogen atoms are replaced by inorganic or organic radicals, which may also contain azo groups, or partly by inorganic and partly by organic radicals. If several organic radicals are present, the said radicals may be the same or different ones. Among the radicals of amines which are capable of forming azo dyestuffs are those which contain a further diazotisable amino group or a group, which eventually can be converted into such a group by saponification or reduction, or substituents enabling the coupling with suitable diazo components. In this case the coupling may be carried out insubstance or on the fibre. Of course, the amines or aminoazo compounds, which must be introduced into the condensation product of the above described general formula, must contain no groupings suitable for metallisation on the fibre or in substance.

The new dyestuffs obtainable according to this invention are direct cellulosic dyestuffs which, in generaLare distinguished by a good drawing power and by a good fastness to water and to washing even by direct dyeing. Surprisingly in the mostcases fastness to water and to washing 10 Claims. (Cl. 260153) a a 2 are considerably improved by an after-treatment with a, little quantity of formaldehyde.

According to the condensation components 7 used in accordance with the invention, which offers numerous possibilities of variation, dyestuffs can be produced which dye cellulosic fibres especially in yellow, orange, red, violet and brown shades and whichare suitable for diazotation and coupling, for coupling with diazotised amines, for the after-treatment with formaldehyde. Thus, difierent types of after-treatment dyestuffs can be prepared, whose after-treated dyeings are distinguished by good to very good fastness properties in the moist state. Finally, there maybe stated that especially the dyestuffs suitable for after-treatment with formaldehyde show the valuable properties that they do not tint animal fibres to any considerable extent so that, in combination with suitable wool dyestuffs, the said dyestuffs are very valuable for dyeing mixtures and mixed fabrics from cellulosic fibres and animal fibres.

The following examples and tables will illustrate theinvention; of course, the invention is not to. be limited to these examples and tables, wherein the parts are by weight.

Example 1 37 parts of cyanuric chloride in form of a fine aqueous suspension are caused to react in a neutral reaction medium with a neutral solution of 37 parts of 4:4diamino stilbene-2:2'

disulfonic acid at 0-4 C. The diprimary condissolving in water with a yellow coloration and dyeing cellulosic fibres in yellow shades of good light-fastness. By :an after-treatment with formaldehyde on the fibre the fastness properties in the-moiststate are considerably improved.

Example 2 37 parts of cyanuric chloride are interacted with 37 parts of 4:4'-diaminostilbene-2:2- disulfonic acid thus giving the diprimary condensation product. Both the remaining halogen atoms are exchanged in the known manner by 92.8 parts of the monoazo dyestufi obtainable from diazotised 2-aminonaphthalene-4:8-disulfonic acid and 1-amino-3-acetaminobenzene. The ditertiary condensation product is produced by causing the obtained product to react on the boiling water-bath with 25.8 parts of aniline hydrochloride and with 60 parts of crystallised sodium acetate.

The dried dyestufi is an orange colored powder dissolving in water with an orange coloration and dyeing cellulosic fibres in reddish yellow shades of good fastn-ess properties in the moist state and of good light-fastness. By an after-treatment with formaldehyde the fastness in the moist state can still further be improved.

Example 3 The condensation product from 3'7 parts of cyanuric chloride and 37 parts of 4:4-diaminostil bene-2:2-disulfonic acid is caused to react in the usual way with 54.2 parts of 4-amino-3- methoxy-l:1-azobenzene-3'-carboxylic acid. The ditertiary condensation product is obtained by a iurthercondensation at 85-95 C. with 30 parts of 3-acetamino-l-aminobenzene in the presence of 30 parts of crystallised sodium acetate.

The dyestuff thus obtained is a brown powder dissolving in waterwith ayellow coloration and dyeing cellulosic fibres in yellow shades of good iastness properties in the moist state which, by

an after-treatment with formaldehyde, can still be improved.

If the acetyl groups of the dyestufi aresaponiness to water and washing are obtained.

Example 4 The condensation product obtainable from 37 parts of cyanuric chloride andS'lparts of 4-4;- diaminostilbene-Z:2'-disulf0nic acid is further condensed with 124.2, parts of the monoazo dyestuff obtainable from 1-diazo-8-(p-toluene sulfo) hydroxynaphthalene-3:6-disulfonic acid and '1- amino-3-methyl-6-methoxybenzene .Both the remaining chlorine atoms are caused to react with 25.8 parts of aniline hydrochloride and with 60 parts of crystallised sodium acetate. The ditertiary condensation product is saltedout, then the p-toluene sulfo group is split off in an alkaline solution and the dyestuff is isolated.

The dried dyestuff is a dark-red powder dis-1 solving in water with a red coloration and dyeing cellulosic fibres in red shades. By an after-v treatment with formaldehyde one obtains dyeings of good fastness properties to water and to washing.

Example 5 of the reaction the mixture is further condensed with 124.1 parts of the monoazo dyestuff obtainable from 1-diazo-8-(p-toluene sulfo)-hydroxynaphthalene-3:S-disulfonic acid and l-amino- 3-methy1-6-methoxybenzene, The ditertiary condensation product is obtained by inter-action with 25.8 parts of aniline hydrochloride and parts of crystalline sodium acetate.

The dried dyestufi is a red powder dissolving in water with a red coloration and dyeing cellulosic fibres in red shades of good fastness properties to water, washing and to light. By an after-treatment with formaldehyde the fastness properties in the moist state are still improved.

Example 6' If the disecondary condensation product obtainable as described in Example 4 from two moles of cyanuric chloride, 1 mole of 4:4- diaminostilbene-Z:2'-disulfonic acid and 2 moles of .the monoazo dyestuff from 1-diazo-8-(ptoluene sulfo) -hydroxynaphthalene-3 Z 6-dissu1- ionic acid and 1-amino-3-methyl-6-methoxybenzene is condensed in the third stage with 2 moles of 3-aminoacetanilide and saponified, there will'be obtained a dyestuff with similar properties. This dyestufi can, moreover, be diazotised and developed on the fibre; thus, when after-treating for example with B-naphthol, highly yellowish red shades of good fastness properties to water and to washing are obtained.

Example 7 The diprimary condensation product from 37 parts of cyanuric chloride and 29.8 parts of 4 4' -diaminostilbene-3 3-dicarboxylic acid is caused to react in the usual manner with 73.9 parts of 4-amino-2-acetamino-l:1'-azobenzene 4'-ch1orosulfonic acid-(3') to give the disecondary condensation product which is further condensed with 25.8 parts of aniline hydrochloride and with 60 parts of crystallised sodium acetate.

The dried dyestuff is a yellowish red powder dissolving in water with a yellowish orange coloration and dyeing cellulosic fibres in reddish yellow shades of good fastness to light, Washing and to water. By an after-treatment with formaldehyde the fastness properties in the moist state can still be improved.

' Example 8 By condensing 37 parts of cyanuric chloride in the usual way with 3'? parts of 4:4 -diaminostilbene-2:2'-disulfonic acid, transforming this condensation product with 73.9 parts of 4-amin0- acetamino-l 1 -azobenzene-4-ch1oro-3"- sulfonic acid into the disecondary condensation product and by further condensing with 28.5 parts of 1-chloro-2:4-diaminobenzene a dyestuff is obtained which dissolves in water with an orange yellowcoloration. It dyes cellulosic fibres in reddish-yellow shades, can be diazotised on the fibre and yields, when developed with phenyl methyl pyrazolone, reddish-yellow dyeings of good washing-and water-fastness.

Example 9 When 37 parts of cyanuric chloride are condensed with 37 parts of 4:4'-diaminostilbene disulfonic acid and subsequently with 47.8 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid and when both the tertiary chlorine atoms are interacted with 25.8 parts of aniline hydrochloride and with 60 parts of crystalline sodium acetate, a bri ht grey substance is obtained.

The condensation product can be applied to cellulosic fibres according to the usual dyeing methods andbe developed with diazotised p-nitraniline or with other diazo compounds. Thus orange to red shades of good fastness properties in the moist state are obtained.

Example 10 37 parts of cyanuric chloride and 3'7 parts of 4:4-diaminostilbene-2:2-disulfonic acid are interacted in the usual manner to give the diprimary condensation product. Then the product is condensed with 89.4 parts of the disazo dyestufi obtainable in a known manner from diazotised 4-amino-1:1'-azobenzene and 2-amino-5-hydroxynaphth-alene-7-sulfonic acid and finally the ditertiary condensation product is produced by interaction with 34.6 parts of metanilic acid.

The dried dyestuff is a dark red powder dissolving in water with a red coloration and dyeing cellulosic fibres in bluish-red shades which, when aftertreated with formaldehyde, possess improved fastness properties to washing.

Example 11 The condensation product obtainable analogously to Example 10 from 2 moles of cyanuric chloride, 1 mole of 4:4'-diaminosti1bene-2:2'- disulfonic acid, 2 moles of 2-amino-5-hydroxynaphthalene-7-sulfom'c acid and 2 moles of aniline is coupled with diazotised 4-amino-1:l'-azobenzene in a slightly alkaline solution.

The dried dyestufi' is a dark red powder which dissolves in water with a red coloration and which dyes cellulosic fibres in bluish-red shades. By an aftertreatment with formaldehyde the fastness properties the moist state may still be improved.

Example 12 ,The condensation product from 37 parts of cyanuric chloride and 37 parts of 4:4'-diaminostilbene-'2:2-disulfonic acid is condensed in a known manner with 75.6 parts of 4-amino-2- methyl- 6 --methoxy- 4 -acetamino1 1'-azobenzene-'-sulfonic acid thus giving the disecondary condensation product. The remaining chlorine atoms are caused to react with 25.8 parts of aniline hydrochloride and with 60parts of crystalline sodium acetate and the acetyl group is saponified in amalkaline solution, for instance as described inExample 3:.

:Thedn'ed dyestuff is a yellowish-orange powder, soluble in water with an, orange coloration and dyeing cellulosic fibres in yellowish-orange shades. By diazotation and coupling with phenyl methyl pyrazolone deep orange dyeings of good fastness properties in the moist state are obtained.

Example 13 37 parts of cyanuric chloride and 37 parts of 4:4'-diaminostilbene-2:2-disulfonic acid are co densed inthe usual manner and the diprimary condensation product is caused to react with 621 parts of the monoazo dyestufl obtainable from l-diazma- (p-toluene sulfo) hydroxynaphthalene-3 zfi disulfonic acid and 1-amino-3-methy1- fi-methoxybenzene. The remaining chlorine hydrochloride and with 90 parts of crystallised sodium acetate. After having split off the toluene sulfo group the dyestuif is obtained in form of a dark red powder. It dissolves in water with a red coloration and dyes cellulosic fibres in red shades of good fastness properties in the moist state, which properties can further be improved by a treatment with formaldehyde.

A similar product may be obtained for instance, if the diprimary condensation product is brought to interaction first with 12.9 parts of aniline hydrochloride and 30 parts of crystallised sodium acetate, then with the above described monoazo dyestuff and finally further condensed with 28.6 parts of monomethylaniline hydrochloride and 60 parts of crystallised sodium acetate.

Ercdmple 14 The diprimary condensation product from 37 parts of cyanuric chloride and 37 parts of 4:4- diaminostilbene-Z:2-disulfonic acid is first condensed with 84.2 parts of the monoazo dyestuff obtainable from diazotised 2-naphthylamine-4z8- disulfonic acid and m-toluidine and then with 38.7 parts of aniline hydrochloride and with parts of crystallised sodium acetate. The dried dyestufi" is a brown powder dissolving in water with a yellow coloration and dyeing cellulosic fibres in yellow shades of good fastness to washing and to water. The fastness properties .in the moist state can still further be improved by an after-treatment with formaldehyde.

Example 15 37 parts of cyanuric chloride and 37 parts of 4 :4 -diaminostilbene-2 2 -disulfonic acid are condensed thus producing the diprimary condensation product. Then this is further condensed with 35.8 parts of 3-aminobenzoyl-2-amino-5- naphthol-7-sulfonic acid. When the interaction has completed the remaining halogen atoms are replaced by the 1:3-diamino-4-chlorobenzene radical. After isolation and drying a bright powder is obtained. By coupling of the latterwith 27.8 parts of diazotised 4-amino-1:1-azobenzene-4-sulfonic acid in a known manner a dyestufl is produced which dyes cellulosic fibres in red shades and which, when diazotised onthe fibres and after-treated with B--naphthol, gives full red dyeings of good fastness to washing and to water.

The same dyestuif may also be obtained, when, in the second stage, the condensation is first efiected with the disa'zo dyestuif obtainable from diazotised 4-amino- 1:1-azobenzene-4-sulionic acid and from 3-aminobenzoyl-2-amino-5-naphthol-7-sulfonic acid and subsequently with 1:3- diaminol-chlorobenzene in order to produce the ditertiary condensation product.

The following tables contain further dyestuffs obtainable according to this invention. In these tables only the compounds corresponding to the components A and B of the dyestuffs having the general formula are indicated.

Table I [In the last column the after-treatment methods coming into question are enumerated] No compound A Compound B dyeing tgfigrggllulosic pSSlbllitn%fn%ItQr-tl'e8t 1 4-amin0-1:1-azobenzene-3-su1i0nic acid aniline i. yellow. -r Formaldehyde. 2 4-amino-2-methy1-5-methoxy 1:1'-azobenzene-4-suld do Do.

ionic acid. 3 4-emno-3-methoxy-l:l-azobenzene-3-carboxylic d0 greenish-yellow D0.

aci 4, 4-amino-2-acetamin0-l:1-azobenzene-4-ch10ro-3 do yellow Do.

sulfonic acid. 5"... 4-amino-2-acetamino-1:1-azobenzenc-4-ch10ro-3- ammonia do Do.

sulfonic ci 6-..; 4-amino-2-acetam'mo-1:1-azobenzene-4"chl0r0-3- dimethylamin'e .do Do.

sulfonic acid. 7 4-amino-2-aeetamino-1:1-azobenzol-4-chl0r0-3-sul- 3-aminoacetani1ide.. -do D0.

tonic acid. I I i 8 2-naplhghylamine4z8-d1sulfonic acid --+3-am1noacetreddish-yellow Do.

1 e. 9. Do. 10 Do. 11. Do. d est monomethylauiline Do.

m diazotised p-toluenesulioester of the 1:8-amino-naphtho1-3:G-disulfonic acid and 1- amino-2-methoxy-5-methyl-benzene, saponified.

dimethylainine lzi-diamino-benzene Do. Formaldehyde, develop with nitrite and B- naphthol.

Table II Dyestuffs of the general formula:

What we claim is:

1. A process for the manufacture of a substantivedyestufl consisting in condensing a compound of the formula 0= =c i /O=N\ N O -NH C H=O H- NH-C N O Q N\\ %CHN l X-C NH-C N SOsH S0311 O-N i i N-C B B Y/ a [In the last column the after-treatment methods coming into question are enumerated] dyeing on cellulosic possibility of alter-treat No. compound A compound B es ment 1 4-amno-5-methoxy-1:1-azobenzene-3-carboxylic dimethylamine greenish-yellow Formaldehyde.

aci 2' do aniline do A. Do. 3 do 3-aminoacetanilide do Formaldehyde, saponified, develop with phenylmethyl-pyrazolone. 4 2-naphthylamine-4:8-d1sulfonic acid 3-aminol-chloro-fl:4-diaminobenzcne. reddish-yellow Formaldehyde, develop acetanilide. with phenylmethylpyrazolone. 5 4-amino-4-acetamino-5-methoxy-2-methyl-l:1-azoaniline H yellow Formaldehyde, saponibenzene-3-su1fomc acid. fled, develop with phenylmethyl-pyrazolone. 6 4-amino-2-acetammo-4-chloro-l:1-az0benzene-3'- do do Formaldehyde. sulionic acid.

Table III wherein X stands for a member selected from the Dyestuffs of the general formula: group consistmg of .CH=CH and A B -CH2CH2- j= each Y stands for a halogen atom and each '2 stands for a member selected from the group con- N C-NH OH=CH NHC N 0 sisting of H, -COOH and SO3H, with amines /CN SOSH Q0311 which are free from groupings suitable for me- X X tallization and from enolisable keto groups, at

[In the last column the after-treatment methods coming into question are enumerated] i compound dyeing on ccllupossibility of N compound A compound X losic fibres after-treatment 1 dyestufl from diazotised p-toluene- 4-amino-3-methoxyaniline... yellowish-red... Formaldehyde.

sulfo-ester of the 1:8-amino'naphth01-3z6-disulfonic acid and lamino-2-methoxy-fi-methyl-benzene, saponified.

l:1-azo-benzene-3- carboxylic-acid.

Similar dyestuffs can be obtained, when the 4:4-diaminostilbene-2:2-disulfonic acid used in the above tables is replaced by 4:4'-diaminostilbene-2:2-dicarboxylic acid, by 4:4-diaminosti1- bene or by the corresponding dibenzyl tives.

deriva- 75 of the benzene series.

least one of the said amines being selected from the group consisting of nionoamino monoazo compounds of the benzene series, monoamino monoazo compounds of both the benzene and naphthalene series and monoamino disazo compounds 2. A process for the manufacture of a; substantive dyestufi consisting in condensing a compound of the formula wherein each Y stands for a halogen atom, with amines which are free from groupings suitable for metallization and from enol-isable keto groups, at least one of the said amines being selected from the group consisting of monoamino monoazo compounds of the benzene series, monoamino monoazo compounds of both the benzene and naphthalene series and monoamino disazo compounds of the benzene series.

3. A process for the manufacture of a substantive dyestufl, consisting in condensing acompound of the formula SOaH H038 with the aminoazo dyestuif of the formula CH3 SOaH and with aniline.

4. A process for the manufacture of a substantive dyestuff, consisting in condensing a compound of the formula with the aminoazo dyestufi of the formula 0 OH: 0 0 0H and with 3-acetylamino-l-aminobenzene.

5. A process for the manufacture of a substantive dyestufl', consisting in condensing a comwith the aminoazo dyestufi of the formula 803E NEOOCHa and with 1-ch1oro-2 :4-diaminobenzene.

6. A substantive dyestufi of the formula 10 wherein X stands for a member selected from the group consisting of CH=CH and SOzH R038 A A wherein each A stands for the radical of an amine which is free from groupings suitable for metallization and from enolisable keto groups, at least one of the said amines being selected fromthe group consisting of monoamino monoazo compounds of the benzene series, monoamino monoazo compounds of both the benzene and naphthalene series and monoamino disazo compounds of the benzene series.

8. The substantive dyestufi of the formula being a. brown powder dissolving in water with yellow color and dyeing cellulosic fibres in yellow 7 shades.

11 12 9. The substantive dyestuff of the formula being a brown powder dissolving in water with OOH3 COOH orange yellow coloration and dyeing cellulosic fibres in reddish yellow shades.

I NH- N=N O ERNST KELLER. 5 REINHARD ZWEIDLER.

NC NBC-43% NH OOOH 2 REFERENCES oITEp N=C/ a The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 0H 2,004,250 Schindhelm et a1. June 11, 1935 2,195,788 Schmid Apr. 2, 1940 2,221,360 Schmid Nov. 12, 1940 2,221,361 Schmid Nov. 12, 1940 NH 2,221,362 Schmid Nov, 12,1940 2,270,478 Schmid 12111.20, 1942 N-C 2,283,261 Kaiser May 19, 1942 Xv NECOOH 2,368,844: Keller Feb. 6, 1945 2,399,066 Schmid et a1 Apr. 23', 1946 FOREIGN PATENTS Number Country Date 00113 CODE 25 110,626 Switzerland June 16, 1925 being a brown powder dissolving in water with 110,663 swltzerland June 1925 yellow color and dyeing cellulosic fibres in yellow shades.

10. The substantive dyestuff of the formula NH: NH-C N NH. O O OH;

S OaH H g 40 H N H C O 0 Ha S 0311 ---S 0:11 I /NH N=N C o1 NH o /N NH N=O\ l 

